Polyazo dyestuffs



Patented Aug. 22, 1950 PDLYAZO DYEST-UFFS 74Walter Hanhart, Riehen, Switzerland, -assignor to Cibaiimitedasel,'-Switzerland, a Swssjrm Y Nonrming. Application July-11, 1946,:seria1No.

Y osaol. InlswazerlandJ1x1y261945 fiClal'ms. 1

According to this invention valuable polyazodyestuis are made "byftreatmg aminoaZo-dye-f stuffs `with lpphosgene, and using at least one ami-noazo-dyestuff of' the *fol-lowing- Tor-mula:

' R1-N=N R2-N=NR3NH2 in WhiehRl represents the radical of n ,hydroxyu benzene-orthocarboicylic acid free from sultonic acid groups, R2 a radical .of the benzene series containing a .snlonio acid group. and R-TNHZ the `radicaloi, an.aminefofy .the henzeneseries .ca-

Dable'fof couplinga para-,position withrespect to the amino eroupt British Patentlio. 491,019y describes a process `for the :manufacture V.of .tetraksaZo-.dyestuffs wherein aminodisazo-dyestuis of the general formula jected to aV treatment with fphosgene and which y have as lmiddle componenti) a, sullfonic acid .of the benzene series because disazo-.dyestuisof this kind icannot be preducedbythe :process :described inthe :British pate-nt. The polyazo-.dyestuffs of the present specication, Which are made from disazo-dyestuishaving asmiddle component a sulfonic acid of the benzene series, have-Droperties, .for example, purer tints of the dyeings, which make'them superior tothe disazo-dyestuis ofthe aforementionedritish patent'whose middle component is a member of the benzenefseries whichis-free from any sulfonic acid group.

The amino-disazo-'dyestuffs Vof the above general formula R1-N=VNR2-N=N-R3-NH2 Which-are. tclcesubiected. to. treatment withvphosenerinaybe preparedinthe following manner.: A diazotized 4QL-.rm'lno-."Jr-nitrobenzene.smfonic acid or a diazotized monoacyl-para-phenylenediamine sulfonic acidlis lcoupledy in an alkaline medium. :with .an zlehydroxy-benzene-Zwarboxylic acid. Coupling canlbe zlorolightarmut in .analkm (Cl. ZBO-1617) line medium, preferably one alkaline with sodium carbonate. As `lamino4 nitroloenzene sulfonic acids therev come into consideration lamino-4-nitrobenzeneJZ-sulionic acid and. 1- amino4-nitrobenzene3.-su1onic zacid. .mon-V oacyl-para-phenylenediamine sulfonic acids there may. be used compounds corresponding to theaaforesaid nitro-'compounds .and containing,

instead of the nitro-group, an acylamino group. The .coupling components may .consist of A1--hydroxybenZene-2-.carboxylic acid itself or .substitution .products thereof which are capable of coupling., such -as l -hydroxybenzene-.S-methZrl-2- carboxylic acid. In the resultingmonoazo-dyestul either 4the nitro group is reduced or the acylamino group is hydrolyzed, depending on the starting material used. An appropriate meansjor reducing the nitro group togform theamino group is an K alkali sulfide, for example, sodium sulde. Hydrolysis of the acylamino group may be brought about by treatment with Vdilute caustic alkalis at a, raised temperature, for instance by "boiling with dilute caustic soda solution. vThe aminoazo-dyestue so formed is diazo't'ized and coupled in an acid medium with an amine of the benzene series capable of coupling V'in para-position Withrespect 'tofthe amino group, for example, lamino2-methoxy-5v-methylbenzene; rlamino r3 methylbenzene, .lamino-.2:-5-.dimethexybenzene, l--amino-3-methoxybenzene or ani-- liner. advantageously coupling the latter compou-nd i-nthe form .of ranilinea@tuethaneesulfonic acicL. and subsequently splitting oit the .cv-meth ane-sulfonicfaeid fgroup. t The treatment Vwith phosgene may be Lcarri out in known manner, for example, in an aqueous medium which is maintained alkaline in reaction. Instead of .symmetrical dyestuffs asymmetrical dyestuis maybe made by using a'mixture of different aminoazo-dyestuffs of which at least one must be of thev above deiin'ed general formula.

The dyestui'ls obtained by the process of the invention are suitable for `dyeing and printing a Widey variety of bers, .such as Wool,-si1l and leather, artificial Vn-.lrers of animal materials or superpclyamides, but more especially for dyeing and printingcellulose bers such as cotton, linen, raxnie, hemp ,and also artificial ,silk or staple fibers oi regeneratedv cellulose.. Especially valuable products are obtained lcy treating the .dyestuis of .the invention nksubstance, or in` the dyebath or especially on the fiber with an .agent yielding metal, Aaclyantaseously ,an agent yielding copper. This treatment can be .carried .out by the usual methods.

Especially valuable results are obtained in Example 2 many cases by the dyeing process described in Patent No. 2,148,659, in which the material is dyed and after-treated, for example, with an agent yielding copper, in one and the same bath. For this purpose there are advantageously used agents yielding copper which are stable towards dilute alkalis, for example, complex alkali copper tartrates and the like (see Patent No. 2,185,905). The treatment with an agent yielding metal may lo be carried out partly in substance and partly on the ber (see British Patent No. 516,076).

The dyestuffs of the invention yield, when after-coppered, mainly red dyeings of good fastness, especially to washing and light. l

The following examples illustrate the invention, the parts being by Weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the 33.7 parts of 4-amino4'hydroXy-3'-carboxyazobenzene-Z-sulfonic acid in the form of its sodium salt are dissolved in 500 parts of warm 5 water and after the addition of 7 parts of sodium nitrite poured into a mixture of ice and 46 parts of hydrochloric acid of 30 per cent. strength. After stirring for several hours, the mineral acid is neutralized by the addition of sodium acetate, followed by coupling with a solution of 9.7 parts of aminobenzene containing sodium acetate, which aminobenzene has first been converted in the usualv manner into the w-methane sulfonic acid by means of formaldehyde and bisulte. When coupling is complete, the w-methane-sulfonic acid group is split off by heating with dilute hydrochloric acid. The aminodisaZo-dyestuf Which has precipitated is ltered off, then dissolved in 5000 parts of water to which sodium kogram to the mer: Y carbonate is added and treated with phosgene at Example 1 ll0--50 C. until the amino compound can no longer be detected. The solution must always 33.7 parts of 4-amino-4-hydroXy-3'-carboxy give a slightly alkaline reaction. After cooling 1:1'-azobenzene2su1fonic acid, which has been 1 the precipitated dyestu of the formula Hooro Hoas sosH COOH l l l obtained by coupling, in a medium which is is filtered and dried. The brown-dyestuff powder maintained alkaline with sodium carbonate, dithus obtained dissolves in concentrated sulfuric azotized 1amino-4nitrobenzene2-sulfonic acid aCd t0 give a 101116, in Water t0 l'iVP an Orangewith salicyuc acid 'and reduction of the nitrobrown ooloratlon and dyes vegetable bers in aZo-dyestuff thusobtained with sodium sul'de, Single or double bath after-Copperins processes are dissolved in 500 parts of warm water with Orange-Ted tmts, Whlch are fast t0 Washlngthe addition of sufficient caustic soda solution Example 3 to bring about neutralization, and mixed Ywith 7 parts of sodium nitrite. The resulting solution 337 parts of l'amlno'fl 'hydroxy "carboxy" is introduced, while thoroughly stirring, into a ,f aZOPenZene-Z'Sulfqmc amd. m the form of its mixture of ice and 46 parts of hydrochloric acid O Sodmm Salt are dlssolvd. m 500 parts of Wafrm of 30 per cent' strength, and the Whole is stirred water and after the addition of 7 parts of sodium for severall hours. The resulting product is then tledlcntc nfxtgporlldsfeggs coupled Wlth a Sollttlon m hydrochloric acid of The whole is stirred for several hours'with cool; 14 parts of 1ammo'?'metrtoxy'methylben' 45 ing and then coupled With a hydrochloric acid zene, and neutrallzed with sodlum acetate. The Solution of 12 9 parts of l amino 3 methoxy ben mineral acid tiberateq during the coupling is zene,- the mineral acid being'neutralized by the neutralized with sodium acetate. When the addition of Sodium Metal-,Q When coupling is coupling is complete the suspension iS acdulated complete, the amino-disazo-dyestuff is separated, wlth mmerel acid and then filtered. whereupon 50 then, in the form of its sodium Sau, dissolved in the dyeStUlff iS Converted iIltO its SOdillm Salt- 5000 parts of water and then treated with phos- The latter is dissolved in 5000 parts of water, and gene 9,1-, a temperature 0f 40-50 C, until the treated With DhOSgene at 10--50c C. with the addiamino compound can no longer be detected. The tion of sodium carbonate until unchanged dyesolution must always give a slightly alkaline restui can no longer be detected. The precipiaction. The precipitated dyestuff of the formula nooo Hogs moo Y 00H3 soaH oooH l l I l l tated and dried tetrakisazo-dyestuff of the is ltered and dried. The brown dyestuiT-powformula der thus obtained dissolves in concentrated sul- Hoocli Hogs 00H3 H300 sioni clzooH Ha CH3 Y is a red-brown powder, which dissolves in confuric acid to give a blue, in water to give a browncentrated sulfuric acid with a blue coloration and red coloration, and dyes vegetable bers in sinm water with a red coloration. It dyes cotton by gle or double bath after-coppering processes red the 1- or 2-bath after-coppering process fast tints which are very fast to washing. red tints. E x m Z 4 A similar dyestui is obtained by starting from a p e 4 amino 4- hydroxy 3- carboxy 1:1- azo- 35.1 parts of 4-amino-3'methy1-4'hydroxy benzene-3-sulfonic acid. 75 5' carboxy-azobenzene-Z-sulfonic acid in the ammessi 1forrno its sodium saltaredissolved in 500 parts or double bath after-coppering` processes :fastred or-warm water and Aafter the additionof` `'i parts tints. 1

of sodium -nitritefare `pOuretlfinto-a mixture of tice and 46 partsof hydrochloriceaoid-of 30 per "several hours, thefwhole is-combined with'a hy- Example 6 cent. "strength, -Arter stirring and Acooling for .5 5 3 *parts of sodium salt of the amnodsazm di'ochloric 'acidlfsolution of '14.4 'parts of l-amino- 'dyestu of the formula O Z-methoXy--methylbenzene 'Tliewm'ineral acid OOOH .s 03H 00H3 is neutralized -withf'sodium acetate. *The aminol A disazO-dyestuff is separated when coupling is .10 OEy .NNnGNp NH complete and "is then'fdissolved inthe 'formof its f soduim salt in 5000 parts of'wa'ter and converted l. H3

into the ureaJ in the usual manner by treat- `mentiwith. phosgene ,insliglitly alkaline solution. described in Example 1 and 2.8 parts of the so- The:filteredy a-Iid'dried dyestuff of the formula Adium Salt ofi 4-hydroxyeS'-carboXy-l-aminonooo VHess i oOHs "Haoo sogH OOOH i om v is a brown powder dissolving Vin concentrated azobenzene are dissolved in 1`000 parts of Water sulfuric acid to give a blue, in Water to give a and 'treated in slightly alkaline solution at about `brown-redcoloration and vdyeing vegetablefibers 40 C. withphosgeneuntilthe amino groups have in single or double bath ,a'ft'ei'-coppering ypi'oc- 25 disappeared. The ltered and dried dyestui esses fast bluish red tints. consistingimainly of the compound of the formula HOO? Hotls 00H3 OOOH n Havo I V is a drak powder which dissolves in concentrated Example 5 Y i l sulfuric acid to glve a greenish blue, in water to 5.3 parts Of thevsodium salt of the aminodisgive an Orange b1ue Solution and which dyes azodyestuff of the hformula vegetable bers in single eremiti@ bath after- COOH. eOiH y OOHa .Copperng processes yellowish red tints very fast OH* N: -N=Nw NH Q a Example 7 Y 3HE t 01 part of the dyestui .Obtained as `described described in Example 1, and 5 parts of the -soin Example 1 and having the formula AHOOO SOQH 00H3 OOH@ sOaH COOH dium rsalt of the aminOdisazo-dyestuf ofwtheiore, .Kin the form of its sodium salt) is dissolved in mula l 200 parts of4 water with the addition of 0.2 part COOH SO3H m Y y CH3 55 of sodium carbonate. 10 parts of cotton are enteredatk 30-40 0C., 'the bath is brought to the boil,

| i i OH D.N N N=N smggv 3 parts vof G-Iaubersalt are added, and dyeing is carried on at 90-95D C. for FA hour. There are which is obtainable in the same manner, are disthen added to the bath 10 parts by Volume 0f a solved in 1000 parts of water and treated in solution prepared by dissolving 10 parts of crysslightly alkaline solution at 40-50" C, with phostalline copper sulfate, l2 parts of tartaric acid gene until it is no longer possible to detect any and the quantity 0f CauStC Soda SOllltOIl required unchanged amino compound. The' precipitated for neutralization in 1000 parts of water. Dyeing dyestuff consisting mainly of the compound of is continued for about 1/2 hour longer at 90-95 the formula, 'n C., the material is then rinsed in cold water, and

HOOG HOSIS 00H3 soaH COOH Hz H3 is ltered and dried. The brown dyestui-powsoaped at 50-75 C. in a bath containing, per der thus obtained dissolves in concentrated sulliter, 5 grams of soap and 2 grams of sodium carfuric acid to give a blue, in water to give a brownbonate. A red dyeing is obtained which is fast red coloration and dyes vegetable fibers in single to washing and light.

atraen;

`lll'hatlclaimis: 1. A tetrakisazdyestui of the formula Y wherein R1 and R1 stand for radicals of a hy- `droxybenzene-ortho-carboxylic acid being 'free from sulfonic acid groups, R2 and Rz stand for benzene radicals containing each a sulfonic acid group and Rs-NH- andA -HN-Ra stand for radicals of an amine of the benzene series coupling in para-position to the amino group.

2. A tetrakisazo-dyestuff of the formula wherein R1 stands for the radical of a. hydroxybenzene-ortho-carfboxylic acid being free from sulfonic acic groups, R2 stands for nabenzene radical containing a sulfonic acid group and Ra-NH- stands for the radical of an amine of the benzene series coupling in para-position to the amino group.

HOOG i H v00H5:

Hooc Y HOOG 3. A tetrakisazo-dyestul of the formula.

wherein R1 stands vfor the radical of a hydroxybenzene-otho-carboxylic acid being free from sulfonic acid groups, Rz stands for a benzene radcal containing a sulfonic acid group and Ra-NH- stands for the radical of an amine of the benzene series coupling in para-position to the amino group.

5. The tetrakisazo-dyestuff of the formula H300 SOaH COOH 6. 'I'herdyestuff of the formula soaH' cliooH 7. The dyestuff of theformula SOaH COOH WALTER HANHART.

l REFERENCES cITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Nurnber Name Date 1,573,605 Gunther Feb. 16, 1926 i FOREIGN PATENTS Number Country Date 491,019 Great Britain Aug. 24, 1938 Great Britain Sept. 8, 1943 Certificate of Correction Patent No. 2,519,651 August 22, 1950 WALTER HANHART It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction as follows:

Column 1, line 12, for a read in; column 5, line 12, for soduim read sodium; column 6, line 33, for drak read dark; column 8, line 15, for -otho read ortho; lines 16 and 17, for R2 stands for a benzene radical containing read one a: stands for hydrogen and the other x stands for;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the oase in the Patent Oiloe.

Signed and sealed this 7th day of November, A. D. 1950.

[sub1 THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

7. THE DYESTUFF OF THE FORMULA 